CN101880355A - Preparation and application of Sudan red I molecular imprinted polymeric adsorbent - Google Patents
Preparation and application of Sudan red I molecular imprinted polymeric adsorbent Download PDFInfo
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- CN101880355A CN101880355A CN 201010210778 CN201010210778A CN101880355A CN 101880355 A CN101880355 A CN 101880355A CN 201010210778 CN201010210778 CN 201010210778 CN 201010210778 A CN201010210778 A CN 201010210778A CN 101880355 A CN101880355 A CN 101880355A
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Abstract
The invention discloses a method for preparing a Sudan red I molecular imprinted polymeric adsorbent and application thereof. The method has the main technical characteristics of : adding Sudan red I, 4-vinyl pyridine, azodiisobutyronitrile and ethylene glycol dimethacrylate into a reactor in a certain molar ratio; introducing argon to remove oxygen in a chloroform medium; reacting for 24h at the constant temperature of 60 DEG C to obtain a bulk polymer; grinding the bulk polymer into fine particles; carrying out Soxhlet extraction for 24h with mixed solution of acetic acid and methanol in a volume ratio of 1:9 to remove template Sudan red I molecules; washing off residual organic matter with the methanol; finally eluting the fine particles with water and the methanol; filtering the fine particles to remove superfine particles; and drying the fine particles in vacuum at the temperature of 60 DEG C. The obtained Sudan red I molecular imprinted polymeric adsorbent has the advantages of specific identification ability to Sudan red I, high selectivity, high adsorption rate, high deabsorption performance, high physicochemical stability, high mechanical stability, and regeneration capacity.
Description
Technical field
What the present invention relates to is a kind of preparation method and utilisation technology of molecular imprinted polymeric adsorbent, particularly a kind of Sudan molecules imprinted polymer preparation method and utilisation technology.
Background technology
Sudan red comprises that mainly I, II, III and IV belong to azo class oil soluble industry pigment for four types, is mainly used in the painted of chemicals such as greasepaint, gasoline, floor wax, is classified as one of three class carcinogenss by international cancer research institution (IARC).Countries in the world have all been ordered and have been forbidden Sudan red is applied in the food; And under the ordering about of economic interests, have the people with Sudan red 1 as additive, be used for processed food such as hot sauce, fermented bean curd, to increase the color and luster of its color, the analysing and detecting method of therefore setting up Sudan red in the food accurately and reliably as early as possible is particularly important.
High selectivity material with molecular recognition function is subjected to people's attention always.Molecular imprinting is one of main method of current preparation high selectivity material.Molecularly imprinted polymer (MIP) according to the preparation of this technology has the specific recognition that is similar to antibody or acceptor, can be used to replace antibody or acceptor and is used for immunoassay.1993, Vlatakis etc. made report in this field first.Show predetermined, single-minded recognition performance owing to the three-dimensional arrangement to microsphere has " memory " function, very wide application prospect is arranged in fields such as separation science, biosimulation science.
In molecular imprinting, when contacting with polymer monomer, template molecule (marking molecule) can form the multiple action point, and this effect will be memorized in the polymerization process.After by rights template molecule being removed, just formed the hole that is complementary with the template molecule sterie configuration, have the multiple action site in the polymkeric substance, these holes are similar to the combining site of enzyme or acceptor, microsphere is shown special efficacy selectivity and recognition capability, and its application relates to separation and purification, chemistry and every field such as biosensor and mimetic enzyme catalysis agent.
Synthesizing of domestic Sudan red 1 adsorption functional material, application number is the synthetic method that discloses a kind of finishing Sudan red 1 sorbing material in 200710057147.4 the patent, its claim is the synthetic method of 1. 1 kinds of Sudan red 1 adsorption functional materials, it is characterized in that: the step of its synthetic method is: (1) adds Sudan red 1 number, 3-aminopropyltriethoxywerene werene and methanesulfonic activation silicon ball in acetonitrile solvent, stirring reaction 30～40min under the reflux state, add tetraethoxysilane and acetic acid again, hatch 8～10h down at 50～80 ℃; (2) above-mentioned polymerisate is filtered the back 10～12h that wears out through ethanol under 90～110 ℃ of temperature condition, add hydrochloric acid and ethanol then, suction filtration behind stirring 1.5～2.5h, be washed till neutrality with alkali and secondary deionized water, till being washed till no template molecule with ethanol again, 60～80 ℃ of vacuum-drying 10～12h promptly obtain Sudan red 1 highly selective adsorption functional material.2. the synthetic method of Sudan red 1 adsorption functional material according to claim 1 is characterized in that: described second is fine, the weight ratio of Sudan red 1 and 3-aminopropyltriethoxywerene werene is 18.8: 1: 3.4.3. the synthetic method of Sudan red 1 adsorption functional material according to claim 1 is characterized in that: the mol ratio of described tetraethoxysilane and acetic acid is 6.7: 1.4. the synthetic method of Sudan red 1 adsorption functional material according to claim 1 is characterized in that: described hydrochloric acid and ethanol weight ratio are 1.3: 100.Concrete being applied in the patent do not mentioned.
First half particular content about the preparation method of molecularly imprinted polymer is as follows.At first model substance is dissolved in the solvent (pore former), mixing has the polymerizability functional monomer that can carry out bonded effect group with the part of model substance, forms the complex body of model substance and functional monomer.Afterwards,, add excessive linking agent and polymerization starter, carry out polymerization as inert monomer in order to keep the sequence with model substance bonded functional monomer.In this process, the solvent that is used to dissolve model substance is playing an important role aspect the characteristic of decision synthetic polymer, particularly because polar solvent dissolving polar molecule, can damage model with function monomer between combine.
Preparation for imprinted polymer, when utilizing emulsion or suspension polymerization to prepare imprinted polymer, for the gravitation that prevents between the functional group of monomer or model molecule and water, to act on, need new contact method, a kind of as this contact method, when letex polymerization or suspension polymerization, use does not mix with organic monomer and does not have the dispersion solvent of attractive interaction to replace water with the model molecule.Fluorocarbons solution uses so can be used as dispersion agent when solution polymerization owing to do not mix with most of organic compound.During polymerization, the tensio-active agent of fluorocarbons soln using fluorine class is with monomer, linking agent, model molecule, solvent stable emulsions such as (pore formers), prevent to be used for the effect gravitation between polymeric solvent and the monomeric functional groups, so when the preparation imprinted polymer, to the recognizing site number of model molecule and to the influence of solvent very little [United States Patent (USP) No. 58722198 and No. 5959050].
But fluorocarbons solution price is higher, so increased the expense of preparation, has increased cost to actual production.Therefore, simple, the economic preparation method of fluorocarbons formulations prepared from solutions ion imprinted polymer is not used in exploitation.
Summary of the invention
One of purpose of the present invention provides a kind of preparation method of Sudan molecules I imprinted polymer adsorbent, mainly make the Sudan red I molecular imprinted polymeric that obtains the Sudan red 1 molecule be had recognition capability, adsorptive power as sorbent material, and the general sorbent material height of volume ratio of absorption.
A kind of preparation method of Sudan red I molecular imprinted polymeric adsorbent; characteristics are: proportioning is by following constitutive molar ratio; n Sudan red 1: n4-vinyl pyridine: n Diisopropyl azodicarboxylate: n ethylene glycol dimethacrylate=(1～1.2): (4～4.5): (0.25～0.30): (20～25); argon shield; polyreaction in the chloroform medium, concrete compound method:
(1) takes by weighing 0.50g Sudan red 1 (being dissolved in the 15mL chloroform) and 1.0mL4-vinyl pyridine in reactor, all after the dissolving, feed argon gas 5min and remove oxygen.
(2) add 0.10g Diisopropyl azodicarboxylate and the ultrasonic hydrotropy 15min of 10g ethylene glycol dimethacrylate toward (1) solution again, feed argon gas 10min again and remove oxygen, sealing triangular flask and air are isolated, in 60 ℃ of waters bath with thermostatic control, react 24h, get bulk polymer, polymkeric substance is ground to form particulate.
(3) with volume ratio be 1: 9 acetate and methanol mixed solution soxhlet extraction 24h (promptly not having template molecule), remove residual acetate with methanol wash again.Last water, methanol-eluted fractions are clean, remove by filter fine particle, place 60 ℃ of vacuum drying oven drying for standby.
Another object of the present invention provides a kind of Sudan red I molecular imprinted polymeric adsorbent to the identification of Sudan red 1 molecule and the application in the absorption, characteristics are: with the Sudan red I molecular imprinted polymeric adsorbent for preparing directly in the chloroform medium, by stationary method absorption; Can also be directly in the chloroform medium, by dynamic method absorption with the Sudan red I molecular imprinted polymeric adsorbent for preparing.
Advantage of the present invention and effect are:
(1) to obtain selective absorbent be to contain Sudan red 1 imprinted polymer material in the present invention, form hydrogen bond between the molecule with 4-vinylpridine and Sudan red 1, carry out molecule by the non covalent bond effect and assemble in advance, add linking agent again and adopt the method for mass polymerization to prepare Sudan red I molecular imprinted polymeric.The molecularly imprinted polymer that this method makes has specific hole, and the Sudan red 1 molecule is had special recognition capability, and selectivity is higher, and other molecule is not adsorbed, and elution time is short.
(2) Sudan red I molecular imprinted polymeric adsorbent preparation process of the present invention is simple, and condition is easy to control, and production cost is low.
(3) the present invention prepares Sudan red I molecular imprinted polymeric adsorbent, and good physical and chemical stability and excellent mechanical stability are arranged, and is simple to the Sudan red 1 adsorption operations.
(4) the present invention prepares Sudan red I molecular imprinted polymeric adsorbent high adsorption capacity, efficient height, and it is 49.66mg/g to the Sudan red 1 maximum adsorption capacity, and high adsorption rate can reach 98%.
(5) have regenerative power simultaneously, can use repeatedly more than 10 times.
Embodiment
Embodiment 1
(1) in the triangular flask of tool plug, add 0.50g Sudan red 1 (being dissolved in the 15mL chloroform) and 1.0mL4-vinyl pyridine in reactor, all after the dissolving, feed argon gas 5min and remove oxygen.
(2) add 0.10g Diisopropyl azodicarboxylate and the ultrasonic hydrotropy 15min of 10g ethylene glycol dimethacrylate toward (1) solution again, feed argon gas 10min again and remove oxygen, sealing triangular flask and air are isolated, in 60 ℃ of waters bath with thermostatic control, react 24h, get bulk polymer, polymkeric substance is ground to form particulate.
(3) with volume ratio be 1: 9 acetate and methanol mixed solution soxhlet extraction 48h (promptly not having template molecule), remove residual acetate with methanol wash again.Last water, methanol-eluted fractions are clean, remove by filter fine particle, place 60 ℃ of vacuum drying oven drying for standby.
Embodiment 2
(1) in the triangular flask of tool plug, add 0.50g Sudan red 1 (being dissolved in the 15mL chloroform) and 1.0mL4-vinyl pyridine in reactor, all after the dissolving, feed argon gas 5min and remove oxygen.
(2) add 0.10g Diisopropyl azodicarboxylate and the ultrasonic hydrotropy 15min of 10g ethylene glycol dimethacrylate toward (1) solution again, feed argon gas 10min again and remove oxygen, sealing triangular flask and air are isolated, react 18h in 70 ℃ of waters bath with thermostatic control, get bulk polymer, polymkeric substance is ground to form particulate.
(3) with volume ratio be 1: 9 acetate and methanol mixed solution soxhlet extraction 48h (promptly not having template molecule), remove residual acetate with methanol wash again.Last water, methanol-eluted fractions are clean, remove by filter fine particle, place 60 ℃ of vacuum drying oven drying for standby.
A kind of Sudan red I molecular imprinted polymeric adsorbent application method: a kind of Sudan red I molecular imprinted polymeric that will prepare, by a kind of be static adsorptive method, another kind is a dynamic adsorption method, and the Sudan red 1 molecular adsorption is used.
Measure absorption property with static adsorptive method, get the Sudan red 1 chloroformic solution 10mL of different concns, the Sudan red I molecular imprinted polymeric that adds equivalent under the same conditions, concussion absorption 1h gets clear liquid, with the concentration of Sudan red 1 in the spectrophotometry clear liquid, go out adsorption rate according to Sudan red 1 strength of solution change calculations before and after the absorption.
Measure absorption property with dynamic method, get adsorption column (internal diameter 10mm * high 50mm), the core dividing plate is arranged at the bottom, the dry method Sudan red I molecular imprinted polymeric of packing into.Beat gently make polymkeric substance dress real after, add skim absorbent cotton in the above, with the pre-drip washing of 10mL chloroform, clean the impurity in the post after, standby.Get the Sudan red 1 chloroformic solution of different concns, with the flow velocity of 1mL/min by adsorption column, with the Sudan red 1 on 1: 9 acetate and the methanol mixed eluant solution adsorption column.With the Sudan red 1 amount of adsorbing on spectrophotometry filtered liquid and the post, calculate adsorption rate thus respectively.
Prepare a kind of Sudan red I molecular imprinted polymeric as stated above to the application in the Sudan red 1 molecular adsorption.Its method is:
(1), adopt Sudan red I molecular imprinted polymeric to adsorb with the method for Static Adsorption in one or more the system that contains in the Sudan red 1 sample.The result shows that this polymkeric substance only to the absorption of Sudan red 1 molecular selectivity, does not adsorb other coexisting substances.
Loading capacity to Sudan red 1 is relevant with factors such as Sudan red I molecular imprinted polymeric hole figure place, adsorption temp, solution mediums.
(2) in one or more the system that contains in the Sudan red 1 sample, adopt Sudan red I molecular imprinted polymeric to adopt the method for dynamic adsorption to handle, flow velocity with 1mL/min passes through adsorption column, with the Sudan red 1 on 1: 9 acetate and the methanol mixed eluant solution adsorption column.With the Sudan red 1 amount of adsorbing on spectrophotometry filtered liquid and the post, the result shows that this polymkeric substance does not adsorb other coexisting ions only to the Sudan red 1 selective adsorption respectively.
Loading capacity to Sudan red 1 is relevant with factors such as Sudan red I molecular imprinted polymeric hole figure place, adsorption temp, solution mediums.
The Sudan red I molecular imprinted polymeric that obtains can reach the high adsorption rate of 49.66mg/g to the loading capacity of Sudan red 1 can reach 98%.
Claims (3)
1. Sudan red I molecular imprinted polymeric preparation method; it is characterized in that: synthetic ratio is by following mol ratio; n Sudan red 1: n4-vinyl pyridine: n Diisopropyl azodicarboxylate: n ethylene glycol dimethacrylate=(1～1.2): (4～4.5): (0.25～0.30): (20～25); argon shield; polyreaction in the chloroform medium, the step of its synthetic method is:
(1) Sudan red 1 and 4-vinylpridine all after the dissolving, feed argon gas 5min and remove oxygen in reactor in chloroform solvent.
(2) add Diisopropyl azodicarboxylate and the ultrasonic hydrotropy 15min of ethylene glycol dimethacrylate toward (1) solution again, feed argon gas 10min again and remove oxygen, sealed reactor and air are isolated, in 60 ℃ of waters bath with thermostatic control, react 24h (or reacting 18h in 70 ℃ of constant temperature), get bulk polymer, polymkeric substance is ground to form particulate.
(3) with acetate and methanol mixed solution soxhlet extraction 24h (promptly not having template molecule), remove residual acetate with methanol wash again.Last water, methanol-eluted fractions are clean, sieve and remove fine particle, place 60 ℃ of vacuum drying oven drying for standby.
2. the preparation method of Sudan red I molecular imprinted polymeric selective adsorbent according to claim 1 is characterized in that: argon shield.
3. the preparation method of Sudan red I molecular imprinted polymeric selective adsorbent according to claim 1 is characterized in that: the volume ratio of described acetate and methanol mixed solution is 1: 9.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102432735A (en) * | 2011-08-30 | 2012-05-02 | 嘉兴学院 | Preparation method of magnetic molecularly imprinted polymer for separating/purifying sudan I |
| CN102617813A (en) * | 2012-04-06 | 2012-08-01 | 济南大学 | Preparation and application of sephadex surface apigenin molecular engram sorbing material |
| CN102698720A (en) * | 2012-05-28 | 2012-10-03 | 河海大学 | Method for preparing extraction probe by means of micro-solid phase extraction based on polymer (methacrylic acid-ethyl glycol dimethacrylate) |
| CN103055829A (en) * | 2013-01-17 | 2013-04-24 | 广西民族大学 | Sudan red I molecularly-imprinted solid phase extraction padding, solid phase extraction column as well as preparation method and application of padding |
| CN103059206A (en) * | 2013-01-24 | 2013-04-24 | 东北林业大学 | Methods for preparing and using sudan red magnetic molecularly imprinted polymer |
| CN103087248A (en) * | 2013-02-27 | 2013-05-08 | 福州大学 | Tony red molecular imprinting polymeric material and preparation method thereof |
| CN103524676A (en) * | 2013-08-26 | 2014-01-22 | 陕西师范大学 | Preparation method and application of monolithic 2-[(6-oxo-6H-benzo[c]chroman-3-yl)oxyl] propanoic acid column |
| CN103551125A (en) * | 2013-10-23 | 2014-02-05 | 邵秋荣 | Preparation method of Sudan red II molecular imprinting solid-phase extraction column filling material |
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| CN101091911A (en) * | 2007-04-16 | 2007-12-26 | 天津科技大学 | Method for synthesizing adsorption functional material for number one Sudan red |
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2010
- 2010-06-28 CN CN 201010210778 patent/CN101880355A/en active Pending
Patent Citations (1)
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| CN101091911A (en) * | 2007-04-16 | 2007-12-26 | 天津科技大学 | Method for synthesizing adsorption functional material for number one Sudan red |
Non-Patent Citations (1)
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| 《化学研究与应用》 20080731 徐莉等 分子印迹聚合物固相萃取红椒粉中的苏丹红I 812-813 1-3 第20卷, 第7期 2 * |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102432735A (en) * | 2011-08-30 | 2012-05-02 | 嘉兴学院 | Preparation method of magnetic molecularly imprinted polymer for separating/purifying sudan I |
| CN102617813A (en) * | 2012-04-06 | 2012-08-01 | 济南大学 | Preparation and application of sephadex surface apigenin molecular engram sorbing material |
| CN102617813B (en) * | 2012-04-06 | 2014-06-18 | 济南大学 | Preparation and application of sephadex surface apigenin molecular engram sorbing material |
| CN102698720A (en) * | 2012-05-28 | 2012-10-03 | 河海大学 | Method for preparing extraction probe by means of micro-solid phase extraction based on polymer (methacrylic acid-ethyl glycol dimethacrylate) |
| CN103055829A (en) * | 2013-01-17 | 2013-04-24 | 广西民族大学 | Sudan red I molecularly-imprinted solid phase extraction padding, solid phase extraction column as well as preparation method and application of padding |
| CN103059206A (en) * | 2013-01-24 | 2013-04-24 | 东北林业大学 | Methods for preparing and using sudan red magnetic molecularly imprinted polymer |
| CN103059206B (en) * | 2013-01-24 | 2014-08-06 | 东北林业大学 | Methods for preparing and using sudan red magnetic molecularly imprinted polymer |
| CN103087248A (en) * | 2013-02-27 | 2013-05-08 | 福州大学 | Tony red molecular imprinting polymeric material and preparation method thereof |
| CN103087248B (en) * | 2013-02-27 | 2014-08-27 | 福州大学 | Tony red molecular imprinting polymeric material and preparation method thereof |
| CN103524676A (en) * | 2013-08-26 | 2014-01-22 | 陕西师范大学 | Preparation method and application of monolithic 2-[(6-oxo-6H-benzo[c]chroman-3-yl)oxyl] propanoic acid column |
| CN103524676B (en) * | 2013-08-26 | 2014-09-17 | 陕西师范大学 | Preparation method and application of monolithic 2-[(6-oxo-6H-benzo[c]chroman-3-yl)oxyl] propanoic acid column |
| CN103551125A (en) * | 2013-10-23 | 2014-02-05 | 邵秋荣 | Preparation method of Sudan red II molecular imprinting solid-phase extraction column filling material |
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Open date: 20101110 |